US4308402A - Process for methyl-capped alkoxylates - Google Patents

Process for methyl-capped alkoxylates Download PDF

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US4308402A
US4308402A US06/096,122 US9612279A US4308402A US 4308402 A US4308402 A US 4308402A US 9612279 A US9612279 A US 9612279A US 4308402 A US4308402 A US 4308402A
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sub
nickel
methyl
catalyst
process according
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Charles L. Edwards
Andrea Sanders
Lynn H. Slaugh
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Shell USA Inc
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Shell Oil Co
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Priority to CA000359555A priority patent/CA1155462A/fr
Priority to DE8080201022T priority patent/DE3064315D1/de
Priority to EP80201022A priority patent/EP0030397B1/fr
Priority to JP16147080A priority patent/JPS5686126A/ja
Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: EDWARDS, CHARLES L., SANDERS, ANDREA, SLAUGH, LYNN H.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds

Definitions

  • This invention relates to a process for the treatment of alkoxyalkanols. More particularly, this invention is directed toward a process for the cleavage of a terminal --CH 2 OH moiety from an alkoxyalkanol at elevated temperatures in the presence of a catalytically effective amount of heterogeneous nickel. The resulting compounds are referred to herein as methyl-capped alkoxylates.
  • Methyl-capped alkoxylates find use as solvents or as low foam detergents for industrial applications. Since these detergents are composed only of the elements carbon, hydrogen and oxygen, they do not pose the environmental problems which stem from detergents containing such heteroatoms as nitrogen, sulfur or phosphorus. However, in the production of the methyl-capped alkoxylates, the ether linkages in the alkoxyalkanol starting materials degrade easily at elevated temperatures; a mild, selective process for production of the methyl-capped alkoxylates is thus of commercial interest.
  • U.S. Pat. No. 3,894,107 discloses the conversion of alcohols to hydrocarbons over a zeolite catalyst impregnated with a metal cation from Groups I-VIII.
  • U.S. Pat. No. 3,920,766 teaches the conversion by simultaneous dehydration and hydrogenation of t-butanol to isobutane over a supported nickel catalyst. Neither of these patents disclose a process which yields a product with one less carbon atom than the reactant alcohol.
  • U.S. Pat. No. 3,501,546 discloses the conversion of alcohols with n carbon atoms to hydrocarbons with (n-1) and (2n-1) carbon atoms over a palladium on titanium dioxide catalyst. The presence of water is said to favor products with (2n-1) carbon atoms.
  • U.S. Pat. No. 4,139,496 teaches the steam dealkylation of alkyl-aromatic hydrocarbons over a supported alumina catalyst containing oxides of nickel, potassium and chromium, with at least a portion of the nickel being in the form of free metal.
  • n is an integer of from 1 to 12
  • R is an alkyl group of 1 to 22 carbon atoms and R' is hydrogen or methyl, with the proviso that when n is an integer of greater than 1, R' may represent mixtures of hydrogen and methyl.
  • the process comprises reacting an alkoxyalkanol of formula (I) at elevated temperatures in the presence of a catalytically effective amount of heterogeneous nickel. The process converts the alkoxyalkanol with high selectivity and yield, and substantially without thermal degradation of the ether linkages, to a methyl-capped alkoxylate of the formula:
  • R, R' and n have the same meanings as above.
  • Preferred alkoxyalkanol reactants of formula (I) above are compounds wherein R is alkyl of 9 to 22 carbon atoms, more preferably 12 to 15 carbon atoms, R' is hydrogen or methyl, more preferably hydrogen, and n is an integer of from 1 to 12, more preferably from 2 to 9, and most preferably from 3 to 6.
  • the most preferred alkoxyalkanol reactant corresponds to formula (I) wherein R is alkyl of 12 to 15 carbon atoms, R' is hydrogen and n is an integer from 3 to 6.
  • the R group may be optionally substituted with any substituent which does not interfere with the cleavage of the terminal CH 2 OH moiety, e.g.
  • R represents an alkyl or aryl group of up to 20 carbon atoms.
  • R' group can be hydrogen or methyl with the proviso that when n is an integer of greater than one, R' may represent mixtures of hydrogen and methyl.
  • straight ethoxylates, straight propoxylates or mixed ethoxylate-propoxylate detergent alcohols are commercially available. The process is particularly suited to the detergent range ethoxylated or propoxylated alcohols with the alkyl chains (R) preferred above of 9 to 22 carbon atoms.
  • Others may be readily prepared by methods known in the art, such as the reaction of a detergent range alcohol with ethylene oxide in the presence of a base. The reactants should not contain impurities which would poison the nickel catalyst.
  • alkoxyalkanol reactants are of formula (I) above, wherein R is alkyl of 1 to 8 carbon atoms, more preferably one to two carbon atoms, R' is hydrogen or methyl, more preferably hydrogen, and n is an integer from 1 to 4, more preferably the integer one.
  • R is alkyl of 1 to 8 carbon atoms, more preferably one to two carbon atoms
  • R' is hydrogen or methyl, more preferably hydrogen
  • n is an integer from 1 to 4, more preferably the integer one.
  • the most preferred alkoxyalkanol reactant when a product useful as a solvent is desired corresponds to formula (I) wherein R is methyl, R' is hydrogen and n is one, commonly known as methyl carbitol.
  • the methyl-capped alkoxylate product from this preferred reactant is glyme, or 1,2-dimethoxyethane.
  • the reaction is carried out at elevated temperatures.
  • temperatures of from about 150° to 270° C. are preferred, with 200° to 250° C. more preferred and 225° to 250° C. most preferred.
  • temperatures of from about 150° C. to about 250° C. are preferred, with 180° C. to 250° C. more preferred.
  • the fixed bed reaction vessel is suitably heated to the desired temperature.
  • higher temperatures may increase the percent conversion of the alkoxyalkanol reactant, but also serve to reduce selectively and increase unwanted side reactions. In no case should a temperature be used which substantially degrades the ether linkages of the reactant or the methyl-capped alkoxylate product.
  • the process is optionally and preferably carried out in the presence of water.
  • the amount of water added may vary widely; preferably, it may vary from about 15 to about 50 percent by volume of the reactant feed.
  • the water may be mixed with the alkoxyalkanol feedstock if the resulting mixture is homogeneous or, particularly in cases where larger volumes of water (i.e. 50% or more) are used and/or gel formation occurs, the water may be separately pumped directly into the reaction vessel.
  • the presence of water generally improves the selectivity and/or activity of the catalyst used in the process.
  • the catalyst utilized is heterogeneous nickel metal, either the metal alone or, more preferably, supported on an inert refractory support with a surface area of at least 1 square meter per gram. At least some, and more preferably substantially all, of the nickel must be in its reduced (metallic) state prior to use in the process.
  • a wide variety of such supported and unsupported nickel catalysts are commercially available and their preparation is described in the art relating to such areas as oligomerization or hydrogenation. Prior to use in the process of this invention, the commercially obtained catalysts are suitably treated and/or activated with hydrogen according to the manufacturer's specifications. Catalysts otherwise prepared are reduced in a conventional manner; the supported catalysts are generally calcined with air and reduced at elevated temperatures with hydrogen prior to use. Thus, at least in the case of a supported catalyst, the portion, if any, of the nickel not present in its reduced (metallic) state will generally be present in its oxide form.
  • nickel-containing compounds may be used to deposit the nickel on the support, with those in which the nickel is more readily reduced being preferred.
  • suitable water soluble nickel-containing compounds include nickel nitrate, nickel sulfate and nickel acetate, with nickel nitrate being preferred.
  • nickel halides or sulfides, especially nickel fluoride is to be avoided since such compounds are more difficult to reduce and are believed, in some cases, to affect the support or deactivate the catalyst.
  • the water soluble nickel-containing compounds are preferred in connection with the supported catalysts for reasons of economy and convenience, other nickel-containing compounds may be used.
  • organonickel compounds such as nickel tetracarbonyl may be employed and are deposited on the support using a suitable solvent, e.g.
  • toluene there may optionally be metal(s) other than nickel deposited on the support; among such other metal(s), chromium and/or zinc are preferred.
  • metal(s) other than nickel deposited on the support among such other metal(s), chromium and/or zinc are preferred.
  • additional metal(s) is preferred in the preparation of products useful as solvents, e.g. glyme.
  • a Ni/Cr/Zn supported catalyst is preferred for the preparation of glyme from methyl carbitol.
  • any additional metal(s) which deactivate the catalyst is to be avoided.
  • Amounts of nickel present on the support are not critical, although amounts from about 5 to about 70 weight-percent (wt-%) of nickel are preferred.
  • the commercially obtained catalysts commonly contain from about 40 to about 70 wt-% nickel.
  • Catalysts otherwise prepared, such as nickel on various aluminas typically contain from about 5 to about 15 wt-% nickel.
  • Supported catalysts wherein metal(s) other than nickel are additionally present typically contain nickel loadings of 10 wt-% or less; the amount(s) of additional metal(s) are again not critical, but are typically each present in amounts less than about 6 wt-%.
  • the nickel is deposited on a suitable inert refractory support with a surface area of at least 1 square meters per gram.
  • Supports with moderate surface areas have been found to result in higher catalyst selectivity and/or activity.
  • preferred surface areas may vary depending on the nickel loading to be deposited on the support, in general those supports with surface areas from about 9 to about 270 square meters per gram (m 2 /g) are preferred, with about 9 to about 160 m 2 /g more preferred, and about 59 to about 135 m 2 /g most preferred.
  • a catalyst prepared on an alpha-alumina support with a surface area of 0.2 m 2 /g is essentially inactive in the process.
  • Highly acidic supports e.g.
  • MSA-3 a silica-alumina type support
  • MSA-3 a silica-alumina type support
  • the support chosen is not critical and a wide variety of materials may be employed, many of which are commercially available.
  • suitable supports include moderate surface area aluminas, silicas, kieselguhr, aluminosilicates which are not highly acidic and activated carbon.
  • Examples of commercially available supported nickel catalysts, with the surface area of the support in m 2 /g following in parentheses, include Harshaw 1404T (125), Gridler G87RS (46) and Calsicat E-230T (160). The support in all cases should be inert to the reaction conditions.
  • the surface area should again be at least 1 square meter per gram, with surface areas from about 100 to about 270 m 2 /g preferred.
  • the preferred unsupported catalyst is Raney nickel.
  • the reaction may be carried out batchwise or continuously, with the continuous process being preferred.
  • the reaction takes place in one or more reaction tubes, with a fixed bed reactor system being preferred. If a plurality of reaction tubes are employed, they may be arranged in parallel or in series; if a series of tubes are employed, means of heating or cooling the reaction tubes are suitably incorporated between said tubes.
  • the catalyst may be regenerated in a conventional manner; the reaction tube(s) will then incorporate means of facilitating the regeneration.
  • the reaction is preferably carried out in the presence of a hydrogen flow to stabilize the catalyst and maintain at least some, more preferably substantially all, of the nickel in its reduced (metallic) state during the reaction.
  • the process is suitably carried out in a stainless steel hot tube reactor in the presence of a continuous hydrogen flow (e.g., approximately 0.1 liters to 10 liters of H 2 per hour per 5 grams of catalyst) to stabilize and maintain the activity of the catalyst.
  • a continuous hydrogen flow e.g., approximately 0.1 liters to 10 liters of H 2 per hour per 5 grams of catalyst
  • the reactant alkoxyalkanols optionally and preferably in the presence of water, are typically passed through the reaction tube containing the catalyst bed at a liquid hourly space velocity (LHSV) from 0.1 to 5.
  • LHSV liquid hourly space velocity
  • the material can be recycled to obtain a higher conversion to product, or in the case of a plurality of reaction tubes arranged in a series, passed through subsequent reaction tube(s). If desired, the lighter products with utilities as ethereal solvents may be further purified by distillation.
  • reaction temperature optional presence or amount of water, the reactant alkoxyalkanol chosen, amount of the nickel catalyst and, additionally in the case of a supported catalyst, the optional presence or amount(s) of other metal(s) in the catalyst, the type of support, the nickel loading on the support and the surface area of the support.
  • the desired products are methyl-capped alkoxylates of formula (II) above. Smaller amounts may also be formed of ethyl-capped alkoxylates of the formula:
  • R, R' and n have the same meanings as above.
  • the presence of such an ethyl-capped alkoxylate is not necessarily detrimental and may in fact prove beneficial.
  • Other byproducts of the reaction may include carbon monoxide, carbon dioxide, alcohols, ethers, and hydrocarbons, as well as minor amounts of unidentified species. While applicants do not wish to be bound by any theory, the reaction is thought to proceed via the following dehydrogenation-decarbonylation scheme: ##STR1## With the addition of water to the reaction medium, carbon dioxide appears as a product. Again, while not wishing to be bound, the presence of water is thought by applicants to facilitate the decarbonylation reaction, thus producing CO 2 instead of CO.
  • the yields of the methyl-capped alkoxylate (II) obtained from the process of this invention are excellent with, under optimum conditions, conversion of the alkoxyalkanol (I) and molar selectivity in excess of 90% obtained.
  • the preferred catalyst comprises 60 to 70 wt-% nickel deposited on an inert refractory support with a surface area of 115 to 135 m 2 /g and preferred reaction conditions include the presence of 50% water by volume, a continuous hydrogen flow and a temperature of approximately 225° C. Harshaw 1404T is an example of this preferred catalyst which is commercially available. The reaction carried out with this combination of parameters affords both high selectivity and conversion. If lower rates of conversion are acceptable, then a catalyst comprising about 6.4 wt-% nickel on alumina with a surface area of approximately 9 m 2 /g affords 100% selectivity to the desired methyl-capped alkoxylate.
  • a catalyst comprising 6.2 wt-% nickel on alumina with a surface area of approximately 100 m 2 /g affords both high selectivity and conversion, with or without the presence of water, at a reaction temperature of about 250° C. and a continuous hydrogen flow.
  • a supported mixed metal catalyst approximately 7.2 wt-% nickel, 1.1 wt-% chromium and 4.4 wt-% zinc deposited on an alumina with a surface area from about 59 to about 100 m 2 /g affords both high selectivity and conversion, in the presence of 50% water by volume, a continous hydrogen flow and a temperature of 250° C.
  • the aforesaid supported mixed metal catalyst is preferred, in the presence of 50% water by volume and a continuous hydrogen flow.
  • selectivity and conversion to any given methyl-capped alkoxylate, including those products having solvent applications may be further optimized through the selection of appropriate reaction parameters such as temperature, pressure and reactor design.
  • this reactant was obtained from Aldrich Chemical Company and purified by passing over a column of activated alumina. Plant hydrogen was used during all reactions to stabilize the catalyst and maintain the nickel in its reduced form. When required, plant distilled water was used in catalyst preparation and with the alkoxyalkanol feed.
  • Harshaw 1404T from Harshaw Chemicals (67 wt-% nickel, 125 m 2 /g surface area, 10 ⁇ 20 mesh)
  • Girdler G-87RS from United Catalysts, Inc. 42 wt-% nickel, 46 m 2 /g surface area
  • Calsicat E-230T from Calsicat Division of Mallinckrodt Chemicals (58 wt-% nickel, 160 m 2 /g surface area).
  • MSA-3 silica-alumina from American Cyanamid.
  • a supported nickel/chromium/zinc catalyst was typically prepared according to the following procedure.
  • a solution of 8.03 grams of Ni(NO 3 ) 2 .6H 2 O, 4.10 grams of Zn(NO 3 ) 2 .6H 2 O and 1.98 grams of Cr(NO 3 ) 2 .9H 2 O dissolved in 12 milliliters of water was added to 24 grams of SCS-59 alumina (dry impregnation). This material was dried in vacuo until free flowing.
  • the solid was added to a hot tube reactor and calcined with air in increments of 100° C. from 25° C. to 500° C. over a period of 4 hours.
  • This catalyst precursor was reduced in a stream of plant hydrogen in increments of 100° C. from 25° C.
  • a supported nickel catalyst was typically prepared according to the following procedure. A solution of 9.15 grams of Ni(NO 3 ) 2 .6H 2 O in 15 milliliters of water was used to impregnate 30 grams of calcined alumina. The material was dried in vacuo until free flowing. This material was calcined in air to 500° C. in increments of 100° C. per 2 hour period and calcined further at 500° C. for 6 hours. The catalyst was cooled to 25° C. and then reduced using 6% hydrogen in nitrogen to 500° C. in increments of 100° C. per 2 hour period, followed by further reduction at 500° C. for 16 hours. Analysis of the catalyst by x-ray fluorescence showed a nickel content of 7.1 weight-percent.
  • NEODOL® ethoxylate 23-3T 10 milliliters of a Harshaw 1404T catalyst were added to a stainless steel vertical hot tube reactor.
  • the catalyst was activated by treatment with hydrogen gas at 225° C. for 16 hours.
  • water was shown to be present, it was mixed with the reactant feed or, especially in cases of larger amounts of water, pumped separately over the catalyst bed to avoid gel formation; water remaining in the product stream was stripped before analysis of products.
  • the product stream passed through a Grove® regulator into a liquid sample collector and hourly samples were taken. The samples were analyzed by C 13 nuclear magnetic resonance spectroscopy. For subsequent runs, the feedstock flow was stopped, the reactor cooled to 25° C. under hydrogen for 16 hours and finally heated up to the desired temperature (e.g. 225° C.) prior to reaction.
  • the desired temperature e.g. 225° C.
  • Example III-3 shows high conversion and selectivity to the desired methyl-capped ethoxylate when 50% by volume of water was added with the reactant.
  • Examples III-9 and III-10 show 100% molar selectivity to the methyl-capped ethoxylate, albeit at lower levels of conversion.
  • Example III Experiments were run according to the general procedure of Example III. Several parameters were varied and the results are shown in Table II. The examples show the generally beneficial effects of using alumina supports with moderate surface areas, at the specified nickel loadings, as well as effects of increased reaction temperatures and the presence of water. Examples IV-10 shows that alpha-alumina, a low surface area support is essentially inactive with the specified nickel loading of 6.7 wt-%. Examples IV-11 and IV-12 show the reduced selectivity obtained with nickel fluoride deposited on a support with a high surface area (MSA-3).
  • Example III Experiments were again run according to the general procedure of Example III, with variation of several parameters. The results are shown in Table III. The examples show the effect of using supported nickel/chromium/zinc catalysts. Examples V-2 -and V-6 show both high conversion and selectivity to the desired methyl-capped product. Example V-7 shows the poor performance of the catalyst when deposited on a higher surface area support.
  • Examples VI-6 and VI-7 show good conversion rates of the methyl carbitol reactant, although Example VI-5, run at a lower temperature, shows higher selectivity to the desired glyme product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
  • Detergent Compositions (AREA)
  • Catalysts (AREA)
US06/096,122 1979-11-20 1979-11-20 Process for methyl-capped alkoxylates Expired - Lifetime US4308402A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US06/096,122 US4308402A (en) 1979-11-20 1979-11-20 Process for methyl-capped alkoxylates
CA000359555A CA1155462A (fr) 1979-11-20 1980-09-04 Methode de preparation de poly(ethers methyliques), et poly(ethers methyliques) ainsi prepares
DE8080201022T DE3064315D1 (en) 1979-11-20 1980-10-27 Process for the preparation of methyl polyethers and methyl polyethers prepared by this process
EP80201022A EP0030397B1 (fr) 1979-11-20 1980-10-27 Procédé de préparation de méthylpolyéthers et méthylpolyéthers préparés par ce procédé
JP16147080A JPS5686126A (en) 1979-11-20 1980-11-18 Manufacture of methylpolyether

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EP (1) EP0030397B1 (fr)
JP (1) JPS5686126A (fr)
CA (1) CA1155462A (fr)
DE (1) DE3064315D1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496632A (en) * 1982-12-16 1985-01-29 Basf Wyandotte Corporation Process for lubricating synthetic fibers
US4659686A (en) * 1983-12-22 1987-04-21 E. I. Du Pont De Nemours And Company Method for treating carbon supports for hydrogenation catalysts
US4806658A (en) * 1982-11-15 1989-02-21 The Dow Chemical Company Cleavage of polyethylene glycol ethers by hydrolysis
US5210322A (en) * 1990-09-20 1993-05-11 Union Carbide Chemicals & Plastics Technology Corporation Processes for the preparation of ethers
US20060089515A1 (en) * 2004-10-21 2006-04-27 Clariant Gmbh Process for continuously preparing alkylene glycol diethers

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1219003A (fr) * 1981-09-30 1987-03-10 William J. Bartley Obtention de monoethyleneglycol et d'ethanol par hydrogenolyse de polyalcoyleneglycols
ZA826898B (en) * 1981-09-30 1983-07-27 Union Carbide Corp Production of monoethylene glycol monomethyl ether,monoethylene from hydrogenolysis of polyalkylene glycols
MY102879A (en) * 1986-08-28 1993-03-31 Colgate Palmolive Co Nonaqueous liquid nonionic laundry detergent composition and method of use.
DE3723323C2 (de) * 1987-07-15 1998-03-12 Henkel Kgaa Hydroxy-Mischether, Verfahren zu deren Herstellung sowie deren Verwendung
JPH11349983A (ja) * 1998-06-10 1999-12-21 Asahi Denka Kogyo Kk 洗浄剤
DE102006010940A1 (de) * 2006-03-09 2007-09-13 Clariant International Limited Verfahren zur Herstellung von längerkettigen Polyalkylenglykoldiethern

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2122129A (en) * 1935-12-24 1938-06-28 Carbide & Carbon Chem Corp Diethyl ether of triethylene glycol
US2886600A (en) * 1957-03-29 1959-05-12 Dow Chemical Co Process for producing isobutyl ethers
US3591641A (en) * 1968-10-28 1971-07-06 Allied Chem Production of dialkyl ethers of polyalkylene glycols

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806658A (en) * 1982-11-15 1989-02-21 The Dow Chemical Company Cleavage of polyethylene glycol ethers by hydrolysis
US4496632A (en) * 1982-12-16 1985-01-29 Basf Wyandotte Corporation Process for lubricating synthetic fibers
US4659686A (en) * 1983-12-22 1987-04-21 E. I. Du Pont De Nemours And Company Method for treating carbon supports for hydrogenation catalysts
US5210322A (en) * 1990-09-20 1993-05-11 Union Carbide Chemicals & Plastics Technology Corporation Processes for the preparation of ethers
US20060089515A1 (en) * 2004-10-21 2006-04-27 Clariant Gmbh Process for continuously preparing alkylene glycol diethers

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DE3064315D1 (en) 1983-08-25
EP0030397A1 (fr) 1981-06-17
JPS6340411B2 (fr) 1988-08-11
EP0030397B1 (fr) 1983-07-20
CA1155462A (fr) 1983-10-18
JPS5686126A (en) 1981-07-13

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